Synthesis and enhanced room-temperature thermoelectric properties of CuO-MWCNT hybrid nanostructured composites.

This work presents the synthesis of novel copper oxide-multiwalled carbon nanotube (CuO-MWCNT) hybrid nanostructured composites and a systematic study of their thermoelectric performance at near-room temperatures as a function of MWCNT wt% in the composite. The CuO-MWCNT hybrid nanostructured composites were synthesized by thermal oxidation of a thin metallic Cu layer pre-deposited on the MWCNT network. This resulted in the complete incorporation of MWCNTs in the nanostructured CuO matrix. The thermoelectric properties of the fabricated CuO-MWCNT composites were compared with the properties of CuO-MWCNT networks prepared by mechanical mixing and with the properties of previously reported thermoelectric [CuO]99.9[SWCNT]0.1 composites. CuO-MWCNT hybrid composites containing MWCNTs below 5 wt% showed an increase in the room-temperature thermoelectric power factor (PF) by ∼2 times compared with a bare CuO nanostructured reference thin film, by 5-50 times compared to mixed CuO-MWCNT networks, and by ∼10 times the PF of [CuO]99.9[SWCNT]0.1. The improvement of the PF was attributed to the changes in charge carrier concentration and mobility due to the processes occurring at the large-area CuO-MWCNT interfaces. The Seebeck coefficient and PF reached by the CuO-MWCNT hybrid nanostructured composites were 688 µV K-1 and ∼4 µW m-1 K-2, which exceeded the recently reported values for similar composites based on MWCNTs and the best near-room temperature inorganic thermoelectric materials such as bismuth and antimony chalcogenides and highlighted the potential of CuO-MWCNT hybrid nanostructured composites for applications related to low-grade waste heat harvesting and conversion to useable electricity.

Enhanced thermoelectric properties of self-assembling ZnO nanowire networks encapsulated in nonconductive polymers.

The near-room temperature thermoelectric properties of self-assembling ZnO nanowire networks before and after encapsulation in nonconductive polymers are studied. ZnO nanowire networks were synthesized via a two-step fabrication technique involving the deposition of metallic Zn networks by thermal evaporation, followed by thermal oxidation. Synthesized ZnO nanowire networks were encapsulated in polyvinyl alcohol (PVA) or commercially available epoxy adhesive. Comparison of electrical resistance and Seebeck coefficient of the ZnO nanowire networks before and after encapsulation showed a significant increase in the network's electrical conductivity accompanied by the increase of its Seebeck coefficient after the encapsulation. The thermoelectric power factor (PF) of the encapsulated ZnO nanowire networks exceeded the PF of bare ZnO networks by ~ 5 and ~ 185 times for PVA- and epoxy-encapsulated samples, respectively, reaching 0.85 µW m-1 K-2 and ZT ~ 3·10-6 at room temperature, which significantly exceeded the PF and ZT values for state-of-the-art non-conductive polymers based thermoelectric flexible films. Mechanisms underlying the improvement of the thermoelectrical properties of ZnO nanowire networks due to their encapsulation are discussed. In addition, encapsulated ZnO nanowire networks showed excellent stability during 100 repetitive bending cycles down to a 5 mm radius, which makes them perspective for the application in flexible thermoelectrics.

Epoxy-Encapsulated ZnO-MWCNT Hybrid Nanocomposites with Enhanced Thermoelectric Performance for Low-Grade Heat-to-Power Conversion.

This work is devoted to the development of epoxy-encapsulated zinc oxide-multiwalled carbon nanotubes (ZnO-MWCNT) hybrid nanostructured composites and the investigation of their thermoelectric performance in relation to the content of MWCNTs in the composite. For the preparation of nanocomposites, self-assembling Zn nanostructured networks were coated with a layer of dispersed MWCNTs and subjected to thermal oxidation. The resulting ZnO-MWCNT hybrid nanostructured networks were encapsulated in commercially available epoxy adhesive. It was found that encapsulation of ZnO-MWCNT hybrid networks in epoxy adhesive resulted in a simultaneous decrease in their electrical resistance by a factor of 20-60 and an increase in the Seebeck coefficient by a factor of 3-15, depending on the MWCNT content. As a result, the thermoelectric power factor of the epoxy-encapsulated ZnO-MWCNTs hybrid networks exceeded that of non-encapsulated networks by more than 3-4 orders of magnitude. This effect was attributed to the ZnO-epoxy interface's unique properties and to the MWCNTs' contribution. The processes underlying such a significant improvement of the properties of ZnO-MWCNT hybrid nanostructured networks after encapsulation in epoxy adhesive are discussed. In addition, a two-leg thermoelectric generator composed of epoxy-encapsulated ZnO-MWCNT hybrid nanocomposite as n-type leg and polydimethylsiloxane-encapsulated CuO-MWCNT hybrid nanocomposite as p-type leg characterized at room temperatures showed better performance at temperature difference 30 °C compared with the similar devices, thus proving the potential of the developed nanocomposites for applications in domestic waste heat conversion devices.

p-Type PVA/MWCNT-Sb2Te3 Composites for Application in Different Types of Flexible Thermoelectric Generators in Combination with n-Type PVA/MWCNT-Bi2Se3 Composites.

This work is devoted to the fabrication of p-type polyvinyl alcohol (PVA)-based flexible thermoelectric composites using multiwall carbon nanotubes-antimony telluride (MWCNT-Sb2Te3) hybrid filler, the study of the thermoelectrical and mechanical properties of these composites, and the application of these composites in two types (planar and radial) of thermoelectric generators (TEG) in combination with the previously reported PVA/MWCNT-Bi2Se3 flexible thermoelectric composites. While the power factors of PVA/MWCNT-Sb2Te3 and PVA/MWCNT-Bi2Se3 composites with 15 wt.% filler were found to be similar, the PVA/MWCNT-Sb2Te3 composite with 25 wt.% filler showed a ~2 times higher power factor in comparison with the PVA/MWCNT-Bi2Se3 composites with 30 wt.% filler, which is attributed to its reduced electrical resistivity. In addition, developed PVA/MWCNT-Sb2Te3 composites showed a superior mechanical, electrical, and thermoelectric stability during 100 consequent bending cycles down to a 3 mm radius, with insignificant fluctuations of the resistance within 0.01% of the initial resistance value of the not bent sample. Demonstrated for the first time, 2-leg TEGs composed from p-type PVA/MWCNT-Sb2Te3 and n-type PVA/MWCNT-Bi2Se3 composites showed a stable performance under different external loads and showed their potential for applications involving low temperature gradients and power requirements in the range of nW.

Multi-technique approach for qualitative and quantitative characterization of furazidin degradation kinetics under alkaline conditions.

Degradation of drug furazidin was studied under different conditions of environmental pH (11-13) and temperature (30-60°C). The novel approach of hybrid hard- and soft-multivariate curve resolution-alternating least squares (HS-MCR-ALS) method was applied to UV-vis spectral data to determine a valid kinetic model and kinetic parameters of the degradation process. The system was found to be comprised of three main species and best characterized by two consecutive first-order reactions. Furazidin degradation rate was found to be highly dependent on the applied environmental conditions, showing more prominent differences between both degradation steps towards higher pH and temperature. Complimentary qualitative analysis of the degradation process was carried out using HPLC-DAD-TOF-MS. Based on the obtained chromatographic and mass spectrometric results, as well as additional computational analysis of the species (theoretical UV-vis spectra calculations utilizing TD-DFT methodology), the operating degradation mechanism was proposed to include formation of a 5-hydroxyfuran derivative, followed by complete hydrolysis of furazidin hydantoin ring.